Dual ion beam ballistic alloying process

ABSTRACT

The invention relates to a low temperature, dual beam vacuum deposition process for forming a hard, stress reduced, ballistically alloyed film such as diamond onto a substrate.

This application is a continuation-in-part of Ser. No. 255,573, now U.S.Pat. No. 4,992,298, filed Oct. 11, 1988.

FIELD OF THE INVENTION

The invention relates to a low temperature, dual beam vacuum depositionprocess for forming a hard, stress reduced, film such as diamond onto aballistically alloyed substrate, the resultant produced article, and theapparatus for fabricating the article.

BACKGROUND OF THE INVENTION

This invention relates to a low temperature process suitable for formingstress-reduced thin films onto a ballistically alloyed substrate in ahigh vacuum, hydrogen-free atmosphere, the coated article formed by theprocess and the accompanying apparatus. More particularly, the inventionrelates to a method which simultaneously utilizes a low energy sputteredbeam and a high energy bombarding beam to ballistically alloy thesurface of a substrate and thereafter simultaneously utilize the lowenergy sputtered beam and a high energy beam to produce thin, pure,stress-reduced hard films such as polycrystalline diamond; the depositedcoatings being bonded to the substrate within a thin, boundary zone inwhich the deposited layer has physically mixed and/or chemically bondedonto the ballistically alloyed surface of the substrate.

BRIEF DISCUSSION OF THE PRIOR ART

U.S. Pat. No. 4,759,948 to Hashimoto discloses a process involvingcodeposition of thin films by utilizing a low energy beam which isproduced by electron gun or resistance heating, and requires a pulsedhigh energy ion beam source produced in a bucket ion source. The processproduces a variety of high quality, strongly adherent films.

U.S. Pat. Nos. 4,437,962 and 4,495,044 to Banks disclose the formationof diamond flakes which can be mixed with a binder to form a compositematerial and an accompanying process for the fabrication of the flakes.In this process, as the deposited material thickens, the internalstresses in the film cause the material to flake and fall away.

U.S. Pat. No. 4,490,229 to Mirtich discloses a dual ion beam process forthe deposition of diamond like films on a substrate. The processutilizes a hollow cathode ion source to produce a beam consisting of amixture of argon and hydrocarbon gases aimed at the substrate to becoated while simultaneously using a second hollow cathode ion source toproduce a pure beam of argon ions which are also aimed at the substrate.This process relies on hydrocarbon gases as the source of the carbon andthus hydrogen is present in the system, which results in stressed,deposited films with less than optimum mechanical properties.

There are a variety of processes which utilize plasma assisted vapordeposition for the formation and deposition of thin, hard films such asdiamond from an electrostatically directed plasma. Examples of suchpatents include U.S. Pat. No. 3,961,103 to Aisenberg; U.S. Pat. No.4,191,735 to Nelson; U.S. Pat. No. 4,444,805 to Corbett; U.S. Pat. No.4,434,188 to Kamo; U.S. Pat. Nos. 4,504,519 and 4,603,082 to Zelez; U.S.Pat. No. 4,725,345 to Sakamoto and U.S. Pat. No. 4,728,229 to Etzkorn.Such processes typically utilize a plasma produced in an arc drivendischarge which is extracted and directed electrostatically into adeposition chamber through a constrictor aperture that allows lowpressure deposition of a film. However, the temperatures involved insuch processes are substantially greater than those utilized by theapplicants. Additionally, the deposited films are not tightly bondedonto the substrates upon which they are coated and therefore lack theimproved bonding of the films produced by the present invention, andalso the films have a much higher amount of internal stresses.Additionally, the presence of undesired hydrogen is found in thesefilms.

Accordingly, there has arisen a need for a process which is particularlycapable of producing a wide variety of film morphologies and theirresulting desired properties, is capable of attaining high depositionrates and can effectively coat a film to a wide variety of materials.Additionally, it is particularly desirable that the process can beconducted below about 300° F. so as not to damage the substrate beingtreated.

SUMMARY OF THE INVENTION

The invention comprises, in a first aspect, a low temperature processfor forming a stress reduced film adhered to a substrate in an evacuatedatmosphere, comprising depositing a layer of a desired non-hydrocarbonsubstance on the substrate with a low energy, sputtered atomic beam;simultaneously exposing the substrate to a first, high energy beam ofinert atoms to grow a ballistically alloyed layer of an initial desiredthickness; reducing the first, high energy beam to a second,substantially less high energy beam to attain a film of a final desiredthickness on the ballistically alloyed surface of the substrate.

The invention comprises, in a second aspect, an article comprising asubstrate having a ballistically alloyed surface and a thin, reduced ininternal stress, amorphous, crystalline or polycrystalline layer of adesired substance deposited thereon; the ballistic alloying occurringwithin a boundary zone in which the thin layer substance has beenphysically mixed and/or chemically bonded with the substrate.

In an apparatus aspect, the invention comprises an apparatus systemcomprising a high vacuum chamber having a first section designed toallow ion beam sputtering of a desired target and a second,interconnected section designed to allow ion assisted deposition of avariety of coatings onto a substrate positioned on a target platenassembly; the chamber adaptable for maintaining a differential vacuumpressure between the sections so as to enable the ion beam sputteringand the ion deposition to proceed simultaneously; a primary, highcurrent, broad beam ion source suitable for sputtering; the sputteringtarget platen assembly angularly rotatable to a desired location; asecondary, high current, broad beam ion source adaptable for operatingat a variety of beam-acceleration energies required for ballisticallyalloying films onto a substrate positioned on a second angularlyrotatable platen assembly; a first film thickness monitor positioned tomonitor the thickness of the film sputtered by the primary ion source; asecond film thickness monitor positioned to monitor the ratio of thearrival rates from the sputtered atomic beam and the secondary ion beam,and control means for controlling the supply of gases utilized by theprimary and secondary ion sources, vacuum pressure in the chamber andchamber temperatures.

BRIEF DESCRIPTION OF DRAWINGS

The objects, advantages and novel features of the invention will be morefully apparent from the following description when read in connectionwith the accompanying drawing set below, wherein:

The drawing is a schematic view of a vacuum chamber system with dual ionbeam sources which is utilized for the deposition of the films on avariety of substrates.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

In describing the preferred embodiment of the invention which isillustrated in the drawing, specific terminology will be resorted to forthe sake of clarity. However, it is not intended that the invention belimited to the specific terms so selected and it is to be understoodthat each specific term includes all technical equivalents which operatein a similar manner to accomplish a similar purpose.

Referring now to the drawing, there is set forth a partitionedevacuation chamber 10 comprised of interconnected sections 12 and 14connected by opening 13 which can be a valve or the like, and which areeach kept at very low pressures during coating of the substrates, i.e.,typically from about 10⁻³ -10⁻⁶ torr. Inside section 12 is positioned aplaten assembly 15 having positioned thereon at least one article, or"substrate" 16 to be coated with a thin film having desired propertieswhich can include hardness, lubricity, superconductivity, oxidationresistance or the like. The platen assembly 15 is water cooled andpreferably has a multi-axis motion control mechanism 17.

In the preferred embodiment of the invention, the substrate 16 is firstexposed to an argon or other suitable inert ion beam 18 which precleansthe substrate surface, i.e., cleans the adsorbed gases and contaminantsfrom the exposed surfaces 16. The precleaning beam 18 preferably has anenergy level ranging from about 100 eV to 2000 eV, preferably 400-1000eV, while the current density of the precleaning beam is typically about0.01 ma./cm² to about 10.0 ma/cm². The argon ion beam 18 is generated bya filament type ion source 20 which is connected to a reservoir whichsupplies the desired gas through a supply tube 22. The inert gas is fedthrough the tube into a main discharge chamber 24, whereupon it isenergized into beam 18.

The ion beam source 20 is preferably a broad beam ion source of theKaufman type, such as is described in "Advances In Electronics andElectron Physics" by H. R. Kaufman, Vol. 36, pp 265-373, 1974. Liquidnitrogen is used in the cold traps of the diffusion pumps of the vacuumsystem during operation of the ion beam source.

Additionally, a second ion beam source 26 for use in section 14 ispreferably of substantially identical construction as ion beam source20. Accordingly, the particular inert gas stream 28 enters into chamber30 of unit 26 in similar fashion as in chamber 24.

Ion beam source 26, upon completion of precleaning of substrate 16, isthen used to produce ion beam 28 which is an inert gas such as argon,although other gases such as neon, krypton, xenon and the like can alsobe utilized. The ion beam 28 strikes an ultra high purity sputteringtarget 31, typically made of 99.999% pure graphite or, if desired,another desired target material such as boron, silicon, a metal or acomposite material such as a refractory carbide, nitride, oxide or thelike. This beam 28 has an energy level of from about 0.5-50 KeV,preferably 1-2 KeV, and a current density ranging from about 0.1-50.0ma/cm². After beam 28 strikes target 31 it produces a sputtered, lowenergy atomic beam 32 comprised of the target atoms, which typicallyhave an energy level ranging from about 1-50 eV for carbon or similartarget materials. The sputtered beam 32 strikes the substrate 16 andforms a thin layer of the sputtered pure atomic materials on the surfaceof the substrate. It is essential in the production of diamond filmsthat the sputtered material cannot be a hydrocarbonaceous substancesince it is imperative that the deposited diamond films be keptcompletely hydrogen free, and thereby are greatly reduced in internalstresses.

Simultaneously with the aforementioned bombardment of the substrate 1 6with beam 32, ion beam source 20 generates a different beam 18, which isa high energy beam of inert atoms, i.e., argon, neon, krypton and xenon,having energies ranging from about 0.1-500 KeV, preferably 0.4-200 KeV.This high energy beam strikes the substrate 16 concurrently with theinitial deposition of the sputtered carbon or other low energy atomspresent in beam 32 and bombards the substrate 16 surface until aballistically alloyed layer ranging in thickness from about 10-2000 Å,preferably about 10-20 Å has been bonded onto the substrate. The term"ballistically alloyed" describes a process of firmly adhering a layeronto a substrate by bombardment of the substrate surface with highenergy particles that become physically mixed and/or chemically bondedwithin the substrate surface. The resulting effect is to grow a surfacelayer having a thickness which extends into the substrate surface ashort distance in a manner similar to a diffusion bonded layer. Thus,the net effect of the high energy bombardment while simultaneouslydepositing a low energy sputtered film is to create a ballisticallybonded layer firmly alloyed into the substrate. The ballistic alloyingoccurs in a thin, e.g., from 10-2000 Å and preferably 10 to 20 Å,boundary zone in which the sputtered layer has become physically mixedand/or chemically bonded with the substrate to produce a strong,effective bond.

Upon completion of the thin bonding layer on the substrate 16, beam 18is transformed from a high energy beam into a substantially lower butstill high energy beam 18 and the two beam deposition process iscontinued until a desired coating upon the substrate is attained.

The second beam 18 which continues the high energy bombardment of thedeposited film on the substrate surface 16 after the aforementionedboundary layer has been formed is preferably the same ion beam of inertatoms which were utilized in the high energy first beam. Typically, thelower high energy beam 18 has an average energy from about 50-500 eV,preferably from about 75-200 eV. As earlier mentioned, this beamreplaces the high energy beam 18 when the ballistically alloyed layerattains a thickness which can typically range from about 10 Å orslightly thicker and effects growing a sputtered deposited film onto thesubstrate.

The resultant coated films range in thickness typically from about100-200,000 Å, and for most applications from about 1000-20,000 Å.Although the process is particularly suitable for forming a variety ofdesired diamond and diamond-like films upon the surface of thesubstrate, a wide variety of other hard films such as pure metallic,nitrides, borides, carbides, oxides and the like can also be sodeposited onto a desired substrate. It is, of course, apparent to oneskilled in the art how changing the particular sputtered materialsand/or reactive or inert gases, as well as the various energy levels ofthe beams, can make the resulting films morphologies different.

Additionally, the process is suitable for treating an extremely widevariety of substrates, such as metals, plastics, glasses, ceramics andthe like, whereas most other prior art systems are quite limited withrespect to the substrates which can be treated. The major reason forthis is that the temperature in the deposition chamber is kept belowabout 300° F., due to the fact that the process is not driven by hightemperature, but is instead a directed kinetic energy process. Thus,although the process creates very high localized temperatures which arecaused by the high energy bombarding "spikes", or atoms, these existonly in such extremely low concentrations upon the surface so that theresultant effect is to create a minimal temperature rise in theimmediate vicinity of the substrate and thus only a very low temperaturerise within the chamber itself occurs.

With respect to the preferred diamond coatings of the invention, theprocess, as indicated above, can both accurately control the thicknessof the deposited diamond film, and also the physical characteristics ofthe diamond films which are so deposited. More particularly, a widevariety of diamond films which exhibit predominately SP₃ bonding ormixtures of SP₂ and SP₃ bonded carbon can be produced. Examples includethe white, clear diamond of intermediate hardness, the harder, nitrogencontaining diamond and also the softer, graphitic type, known as"carbonado" films which exhibit SP₂ bonding. It should be noted that thedeposited films, whether of diamond or diamond-like character aresubstantially continuous polycrystalline films.

Returning to the drawing, evacuation chamber 10 and its respectivesections 12 and 14 are attached to the diffusion or cryo-pumped vacuumsystems through pipes 34 and 36, respectively. Additionally, a suitablefilm measuring thickness device, such as a quartz crystal film thicknessmonitor 38 measures the rate of deposition of the sputtered beam 32 ontosubstrate 16, as does a quartz crystal thin film monitor 40 which isutilized to determine the respective ratios of the various beams 18 and32.

The growth rates of the deposited films are limited only by the speed atwhich carbon or other material can be sputtered onto the surface of thetarget material. Typically for diamond, which has the slowest rate offormation, the rate is typically about 2.0 Å/min, although it can rangefrom about 0.1 Å/min to 10 Å/min. Additionally, as one skilled in theart would realize, the deposition rate for other films which are easierto deposit would usually be substantially higher.

The dual ion beam ballistic alloying process has an additional advantagein that it allows a high degree of control with respect to suchvariables as the initial surface cleaning of the target substrate, thearrival of the deposited carbon or other sputtered material onto thesubstrate surface, the concentration and depth profile of the initialballistically bonded zone in the substrate surface and the carefulcontrol of the resultant diamond or other film morphology during thelater growth phase upon the substrate. Additionally, other gases can beintroduced into the substrate to change the composition of the film toachieve a desired property, i.e., doping the formed films. As mentionedabove, the presence of hydrogen is not permitted in the system unless anexotic film is desired to be made and it is an advantage of theinvention that such hydrogen containing films are not formed except insuch rare situations where desired, thereby substantially reducing theproblem of internal stresses being present in the resultant formedfilms. An additional improvement is the ability to carefully controlboth the respective energies and deposition rates of each of the twobeams which simultaneously strike onto the substrates surface. Thus,through a careful control of the respective parameters of each of thebeams, a wide variety of carefully designed films can be bonded to andgrown upon the substrate.

The process of the invention is particularly suitable for producing awide variety of coated articles. For example, tools, dies, molds,bearings, machine elements, optical lenses and the like are particularlysuitable articles for treatment. Additionally, high technology devicessuch as semiconductors, electronic devices and the like are alsoparticularly adaptable for treatment. The process operates in asubstantially continuous manner as opposed to certain prior art systemswhich require pulse or other continually varying beam deposition systemswhich must operate in such a complex manner in or to function.Additionally, the apparatus utilized in the invention is particularlysuitable for coating substantially larger articles than have heretoforebeen able to be fitted into the particular apparatus which must beutilized.

EXAMPLE 1 Plastic Lens--Coated with Diamond Film

An optical lens molded from polycarbonate plastic is mounted on theplaten 15 in section 12 of chamber 10. A high purity graphite sputteringtarget is placed on a sputtering target platen in section 14 of chamber10. The pressure in both sections of chamber 10 is evacuated to about1×10⁻⁵ torr and the valve connecting sections 12 and 14 is opened. Ionbeam 18, composed of purified Argon gas, is turned on and used topreclean the lens surface prior to film deposition. The ion beam 18current is 100 mA at 400 volts, and is left on to clean the lens surfacefor about 30 minutes during which time about 2000 angstroms of the lenssurface is sputtered away. When the cleaning is completed, the ion beam18 current is lowered to approximately 10 mA with the voltage increasedto 800 volts, and ion beam 28, composed of purified Ar gas, is turned onat a voltage of 800 volts in section 14 of chamber 10. This produces asputtered beam 3 consisting of carbon atoms. The carbon atoms arrivingat the plastic lens surface are ion beam mixed into the surface of thelens for approximately 1/2 hour. The voltage of ion beam 18 is thenreduced to approximately 75 volts and the current level of ion beam 18is adjusted to 10 mA to allow the growth of SP₃ bonded polycrystallinediamond films on the plastic lens surface. The 10 mA for ion beam 18 isadjusted by monitoring film growth rates with thin film sensor 40. Thetemperature rise in the lens remains below 150 degrees F. during allprocessing steps. A continuous polycrystalline diamond film, initiallyion beam mixed into the surface of the plastic lens, is grown on thelens to a thickness of 1000 angstroms at a rate of 2 angstroms perminute. The diamond film thus deposited on the surface of the plasticlens acts as a hard protective layer which increases the resistance ofthe lens to scratching and abrasive wear.

EXAMPLE 2 Metal Mold--Coated with Diamond Film

Using the same apparatus as in Example 1, a metal mold used for moldingof precision glass lenses is mounted to platen 15 in section 12 ofchamber 10. The mold is fabricated from a nickel-based Inconel 718alloy. The molding surface of the mold is highly polished and opticallyreflective. Ion beam 18 is used to preclean (1500 volts) the moldsurface, and then ion beam mix (4000 volts), and grow (200 volts), acontinuous polycrystalline diamond film on the molding surface of themold to a thickness of approximately 1000 angstroms at a rate of 2angstroms per minute. No change in the precision polished surface of themold was evidenced due to the presence of the grown diamond film layer.The diamond film thus deposited on the mold acts both as a hardprotective layer exhibiting much improved abrasive wear resistance, andalso as a chemically inert layer reducing chemical attack of thecritical molding surface by the molten glass.

EXAMPLE 3 Glass Mold--Coated with Diamond Film

Using the same apparatus as in Example 1, a glass mold used for moldingof precision plastic lenses is mounted onto platen 15 in section 12 ofchamber 10. The mold is fabricated from silica glass material. Themolding surface of the mold is highly polished and the mold is opticallytransparent. Ion beam 18 is used to preclean (1000 volts) the moldsurface, and then ion beam mix (2000 volts), and grow (150 volts), acontinuous polycrystalline diamond film on the molding surface of themold to a thickness of approximately 1000 angstroms at a rate of 2angstroms per minute. No change in the precision polished surface of themold was evidenced due to the presence of the grown diamond film layer.The diamond film thus deposited on the mold acts both as a hardprotective layer exhibiting a much improved abrasive wear resistance,and also a lubricating layer which reduces adhesion of cured plastic tothe molding surface thereby improving the surface finish of the moldedplastic lenses.

EXAMPLE 4 Bearing Race--Coated with Silicon Nitride Film

Using the same apparatus as in the prior examples, an inside raceelement of a roller bearing is mounted onto platen 15 in section 12 ofchamber 10. The race element is fabricated from M-50 bearing steel. Thecontacting surface of the race element is highly polished. In thisexample, purified N is substituted for purified Ar in ion beam 18, and apure silicon target is substituted for the graphite target 31, thusproducing a flux (32) of Si atoms when ion beam 28 is turned on (2000volts). Ion beam 18 is used to preclean (1000 volts) the race elementsurface, and then ion beam mix (3000 volts), and grow (100 volts), anamorphous silicon nitride film on the contacting surface of the raceelement to a thickness of approximately 1000 angstroms at a rate of 20angstroms per minute. The operating parameters of ion beam 18 are set to100 volts and 90 mA to achieve this film growth rate. No change in thefinish of the precision polished surface of the race element wasevidenced due to the presence of the grown silicon nitride film layer.The silicon nitride film thus deposited on the race element surface actsboth as a hard protective layer exhibiting much improved abrasive wearresistance, and also as an adhesive force barrier that reduces theadhesive forces between the race element and the balls thereby reducingadhesive wear (galling).

A separate embodiment of this example involves ballistically alloyingand growing a thin diamond film onto the race element. The diamond filmthus deposited not only provides a hard protective layer exhibiting muchimproved abrasive wear resistance but also provides a layer that gettersor maintains the presence and stability of thin hydrocarbon hydrodynamiclubricating layers.

EXAMPLE 5 Scorino Die--Coated with Chromium Nitride Film

Using the same apparatus as in the above mentioned examples, a scoringdie used in the manufacture of seamless aluminum beverage can lids ismounted onto platen 15 in section 12 of chamber 10. The scoring die isfabricated from D-2 tool steel. The knife edge machined into the workingsurface of the scoring die, which scores the can lid at the precisedepth to allow easy opening and at the same time seal and maintain thecontents of the can under pressure, is of precision tolerance and wearsrapidly. In this example, purified N is substituted for purified Ar inion beam 18, and a pure chromium target is substituted for the graphitetarget 31, thus producing a flux (32) of Cr atoms when ion beam 28 isturned on. Ion beam 18 is used to preclean (600 volts) the die surface,and then ion beam mix (2000 volts), and grow (100 volts), an amorphouschromium nitride film on the entire working surface of the scoring die,including the precision knife edge, to a thickness of approximately 1000angstroms at a rate of 10 angstroms per minute. The operating parametersof ion beam 18 are set to 100 volts and 45 mA to achieve this growthrate. No change in the sharpness or toughness of the precision knifeedge on the scoring die was evidenced due to the presence of the grownchromium nitride film layer. The chromium nitride film thus deposited onthe scoring die acts both as a hard protective layer exhibiting muchimproved abrasive wear resistance, and also as an adhesive force barrierthat reduces the adhesive forces between the knife edge and the aluminummaterial being scored, thus reducing aluminum pick-up on the knife edge.

EXAMPLE 6 Alumina Substrate--Coated with Superconducting Film

Using the same apparatus as in the above mentioned examples, an alumina(aluminum oxide) substrate is mounted to platen 15 in section 12 ofchamber 10. In this case the substrate is to be coated with a thin filmof the superconducting material Er₁ Ba₂ Cu₃ O₇ for use as a currentconducting element on the substrate or as an active device such as amagnetic field sensor. Such a film can either be deposited throughappropriate masks as a strip electrode of varying width and length, orin any other pattern desired. In this example, purified Ar is utilizedin ion beam 18, and a composite target of Er₁ Ba₂ Cu₃ O₇ is substitutedfor the graphite target 31, thus producing a flux (32) of Er, Ba, Cu,and O atoms when ion beam 28 is turned on. Also, ion beam 28 is formedwith a mixture of Ne, Ar, and Kr chosen in such proportion (10% Ne, 30%Ar, 60% Kr) so that the atomic weight percentage composition of Er, Ba,Cu and 0 in sputtered flux 32 is the same as that in the sputteringtarget 30. Ion beam 18 is used to preclean (1500 volts) the substratesurface, and then ion beam mix (200,000 volts), and grow (175 volts), acomposite superconducting oxide film is grown on the alumina substrateto a thickness of approximately 1000 angstroms at a rate of 5 angstromsper minute. The operating parameters of ion beam 18 are set to 150 voltsand 25 mA to achieve this film growth rate. To further optimize theoxidation state of the superconducting oxide films and thus the criticaltemperature and transition temperature range, O atoms are incorporatedat a level of between 5% and 10% in ion beam 18. Adhesion to the aluminasubstrate is optimized and the superconducting films will not crack orspall away during cycling to superconducting temperatures.

EXAMPLE 7 Turbine Blade--Coated with Oxidation Resistant Film

Again, using the same apparatus system, a turbine blade for a gasturbine engine is mounted to platen 15 in section 12 of chamber 10. Theturbine blade is fabricated from a nickel-based alloy, Incoloy 901. Theturbine blade must operate at temperatures in excess of 700° C. and itis thus desirable to coat the blade surfaces with an oxidation-resistantresistant material to improve its operating performance and lifetime,with the thermal barrier coating such as Yttria Stabilized Zirconia(YSZ). In this example, purified Ar is utilized in ion beam 18, and acomposite of YSZ is substituted for the graphite target 31, thusproducing a flux (32) of Y, Zr, and O atoms when ion beam 28 is turnedon. Also, ion beam 28 is formed with a mixture of Ne and Kr chosen insuch proportion (20% Ne, 80% Kr) so that the atomic weight compositionof Y, Zr, and O in sputtered flux 32 is the same as in sputtering target30. Ion beam 18 is used to preclean (1000 volts)the blade surface, andthen ion beam mix (2000 volts), and grow (150 volts), the YSZ film isgrown on the Incoloy 901 substrate to a thickness of approximately 1000angstroms at a rate of 5 angstroms per minute. The operating parametersof ion beam 18 are set at 150 volts and 25 mA to achieve this filmgrowth rate. To further optimize the oxide stoichiometry, O atoms areincorporated at a level of between 5% and 10% in ion beam 18. The YSZfilms so-grown exhibit excellent adhesion directly to the Incoloy 901substrate, and cracking and spalling of the films during temperaturecycling is minimized.

EXAMPLE 8 Razor Blades--Coated with Diamond Film

Razor blades, held in bundles with the sharpened cutting edges exposed,are mounted to platen assembly 15 in section 12 of chamber 10. The razorblades are stacked such that both sides of the entire cutting edge ofeach razor blade, approximately 0.0005 inches down from the apex of thecutting edge will be exposed to the energetic ion beams of the process.A high purity graphite sputtering target 31 is placed on sputteringtarget platen in section 14 of chamber 10. The pressure in both sectionsof chamber 10 is evacuated into the low 1E10(⁻⁵) torr range and thevalve between them is opened. Ion beam 18, composed of purified Ar gas,is turned on and used to preclean the exposed cutting surfaces of therazor blades prior to diamond film deposition. Both sides of the cuttingedge of the razor blades are exposed to the Ar sputter cleaning beam byrotating the platen continuously through a full 360 degrees. Ion beam 18current is nominally 100 mA at 800 volts, and is left on to clean theexposed cutting edges of the razor blades for approximately 10 minutesduring which time approximately 10 angstroms of material on the razorblade surface at the cutting edge on both sides is sputtered away. Whenthe cleaning is completed, ion beam 18 current is lowered toapproximately 10 mA with the voltage maintained at 800 volts, and ionbeam 28, composed of purified Ar gas, is turned on in section 12 ofchamber 10. This produces low energy atomic beam 32 consisting of Catoms. The C atoms arriving at the cutting edge of the razor blade areion beam mixed into the surface of the razor blade for approximately 1/2hour. The voltage of ion beam 18 is then reduced to approximately 150volts and the current level of ion beam 18 is adjusted to 10 mA to allowthe growth of SP₃ bonded polycrystalline diamond films on the edges ofthe razor blade. The 10 mA current level for ion beam 18 is determinedby monitoring the film growth rates with thin film sensor 40. Thetemperature rise in the razor blade remains below 90 degrees F. duringall processing steps. A continuous polycrystalline diamond film,initially ion beam mixed into the surface of the razor blade, is grownon the razor blade to a thickness of 300 angstroms at a rate of 2angstroms per minute. The diamond film thus deposited on both sides ofthe cutting edge of the razor blade acts as a hard protective layerincreasing the wear and corrosion resistance of the razor blade. Thediamond film thus deposited also improves the adhesion of additionalteflon layers that are sputter-deposited on the cutting edge of therazor blade providing a smoother cutting surface that lasts longer.

EXAMPLE 9 Magnetic Recording Heads--Coated with Diamond Film

Reading and recording heads for magnetic recording of video and audiosignals are mounted to platen 15 in section 12 of chamber 10. Thereading and recording heads are subjected to abrasive wear during usewhen the metallic oxide coated mylar recording tapes slide across theexposed magnetic core in the reading and recording head. The abrasivewear produces a degradation in the bandwidth response of the heads whichcan be eliminated by coating of the heads with diamond films. A highpurity graphite sputtering target 31 is placed in section 14 of chamber10. The pressure in both sections of chamber 10 is evacuated into thelow 1E10(⁻⁵) torr range and the valve between them is opened. Ion beam18, composed of purified Ar gas, is turned on and used to preclean theactive surfaces of the magnetic heads prior to diamond film deposition.Uniform cleaning is achieved by rotating the platen continuously througha full 360 degrees. Ion beam 18 current is nominally 100 mA at 800volts, and is left on to clean the active surfaces of the magnetic headsfor approximately 10 minutes during which time approximately 10angstroms of material on the surface of the heads is sputtered away.When the cleaning is completed, ion beam 18 current is lowered toapproximately 10 mA with the voltage maintained at 800 volts, and ionbeam 28, composed of purified Ar gas, is turned on in section 12 ofchamber 10. This produces sputtered beam 32 consisting of C atoms. The Catoms arriving at the active surface of the magnetic heads are ion beammixed into the surface of the heads for approximately 1/2 hour. Thevoltage of ion beam 18 is then reduced to approximately 150 volts andthe current level of ion beam 18 is adjusted to 10 mA to allow thegrowth of SP₃ bonded polycrystalline diamond films on the active surfaceof the heads. The 10 mA current level for ion beam 18 is determined bymonitoring the film growth rates with thin film sensor 40. Thetemperature rise in the magnetic heads remains below 90 degrees F.during all processing steps. A continuous polycrystalline diamond film,initially ion beam mixed into the surface of the magnetic heads, isgrown on the heads to a thickness of 300 angstroms at a rate of 2angstroms per minute.

EXAMPLE 10 Ion Beam Enhanced Deposited Chromium Layers

Conventional hard chromium and decorative chromium plated layers aredeposited on component surfaces by electrochemical techniques. Toxicacid and alkali solutions are required for initial surface cleaning andpreparation, and for the actual electrodeposition process. Chromiumlayers cannot be deposited directly on all metals and other materials,and in many cases metallic interlayers like nickel and copper must bedeposited first. The chromium plated components must in general be bakedat temperatures up to 500-1000 degrees F. to relieve internal stressesin the chromium plated layer and optimize layer hardness and adhesion.The ion beam ballistic alloying process can be used to deposit and growchromium layers on the surface of components made from any metallic,glass, plastic, or ceramic material, without the need for intermediatemetallic interlayers, and at low temperature.

As in the above-mentioned example, components to be coated with chromiumlayers are mounted to platen assembly 15 in section 12 of chamber 10. Inthis case a pure Cr target is substituted for the graphite target 31,which produces a beam 32 of Cr atoms when ion beam 28 is turned on.Using the same precleaning, ion beam mixing, and film growth procedures,a metallic chromium film is first ballistically alloyed into, and nextgrown directly on the surfaces of the component to be chromium coated.Chromium layer coating thicknesses of between 5,000 and 20,000 angstromsare achieved at deposition rates of approximately 10 angstroms perminute. The operating parameters of ion beam 18 are set to 150 volts and45 mA to achieve this growth rate. No intermediate metallic interlayersare required, and the chromium layers are grown in compressioneliminating the need for post-deposition baking to relieve residualinternal tensile stresses.

In another embodiment of the procedure, purified N is substituted forpurified Ar in ion beam 18. Using the same precleaning, ion beam mixing,and film growth procedures, a metallic chromium film containing highconcentrations of chromium nitride precipitates is first ballisticallyalloyed into, and next grown on the entire working surface of thecomponent to be coated. The atomic percentage concentration of chromiumnitride precipitates found in the metallic chromium coatings is variedby adjusting the arrival rate of sputtered chromium ions in beam 32 andthe flux rate of N ions in beam 18. Metallic chromium layers containinghigh atomic percentage concentrations of included chromium nitrideprecipitates exhibit properties that include improved resistance toadhesive-type wear. Chromium layer coating thicknesses of between 5,000and 20,000 angstroms are achieved at deposition rates of approximately10 angstroms per minute. No intermediate metallic interlayers arerequired, and the chromium layers are grown in compression eliminatingthe need for post-deposition baking to relieve residual internal tensilestresses.

In a separate embodiment of the above procedures, sputter target 31 andion beam 28 are replaced by a electron gun evaporator which is capableof providing higher flux rates of Cr atoms 32. By increasing the fluxrate of ions in beam 18, much faster growth rates can be achieved (20-50angstroms per minute), and thicker chromium layers can be deposited(20,000-100,000 angstroms).

The following Table is a recapitulation of the beam energies (volts)utilized in Examples 1 through 10 and illustrates the ranges of energiesthat may be utilized to accomplish the present invention.

                                      TABLE                                       __________________________________________________________________________                              Beam Energies (Volts)                               EXAMPLE                                                                              SUBSTRATE FILM     28  18A                                                                              18B   18C                                    __________________________________________________________________________    1      Plastic Lens                                                                            Diamond  800  400                                                                              800   75                                    2      Metal Mold                                                                              Diamond  800 1500                                                                             4000  200                                    3      Glass Mold                                                                              Diamond  800 1000                                                                             2000  150                                    4      Bearing Race                                                                            Silicon Nitride                                                                        2000                                                                              1000                                                                             3000  100                                    5      Scoring Die                                                                             Chromium Nitride                                                                       800  600                                                                             2000  100                                    6      Alumina Substrate                                                                       Superconductor                                                                         800 1500                                                                             200,000                                                                             175                                    7      Turbine Blade                                                                           YSZ      800 1000                                                                             2000  150                                    8      Razor Blades                                                                            Diamond  800  800                                                                              800  150                                    9      Recording Heads                                                                         Diamond  800  80                                                                               800  150                                    10     IBED Chromium                                                                           Chromium,                                                                              Not Specified                                                        Chromium Nitride                                             __________________________________________________________________________     A = Cleaning                                                                  B = Mixing                                                                    C = Thin layer growth                                                    

While certain preferred embodiments of the present invention have beendisclosed in detail, it is to be understood that various modificationsmay be adopted without departing from the spirit of the invention orscope of the following claims.

We claim:
 1. A process for forming a film adhered to a substrate in anevacuated atmosphere comprising:a) cleaning the surface of the substratewith a first energy beam of inert atoms having an energy level in therange from about 100 eV to 2000 eV, b) after said cleaning, sputtering adesired non-hydrocarbon substance within said atmosphere by a secondbeam of inert atoms having an energy of about 1-50 eV/atom and at a rateand in a direction to cause such substance to deposit on said substrate,c) simultaneously with said sputtering, exposing the substrate to saidfirst energy beam of inert atoms at an energy level in the range fromabout 0.1 KeV to 500 KeV to grow a ballistically alloyed layer having athickness of about 10-2000 Å in said substrate, d) subsequently ofexposing the substrate to the first beam and the sputtering, continuingthe sputtering and exposing the substrate to a lower energy beam ofinert atoms from the source of said first beam at an energy level in therange from about 50 eV to 500 eV that will cause the growth of a film ofsaid substance on said substrate to a final desired thickness.
 2. Aprocess according to claim 1 wherein the film is selected from metallic,diamond, nitride, boride, carbide, oxide and diamond-like films.
 3. Aprocess according to claim 2 wherein the film is diamond.
 4. A processaccording to claim 1 wherein the temperature in the evacuated atmosphereis less than about 300° F. and the pressure ranges from about 10⁻³ -10⁻⁶torr.
 5. A process according to claim 1 wherein the substrate isselected from metals, ceramics, glasses and plastics.
 6. A processaccording to claim 1 wherein the first energy beam is selected fromatoms of argon, neon, krypton, and xenon.
 7. A process according toclaim 1 wherein the sputtered ion beam is selected from atoms ofgraphite, boron, silicon, metals, refractory carbides, nitrides oroxides.
 8. A process according to claim 1 wherein the thereofballistically alloyed layer has a thickness ranging from about 10-20 Å.9. A process according to claim 1 wherein the film is deposited at arate of about 0.1 to 10 Å/min.
 10. The process of claim 1 wherein theprocess is conducted in the absence of hydrogen.
 11. The process ofclaim 2 wherein the process is conducted in the absence of hydrogen. 12.The process of claim 4 wherein the process is conducted in the absenceof hydrogen.
 13. The process of claim 5 wherein the process is conductedin the absence of hydrogen.
 14. The process of claim 1 wherein theenergy level of step a) is in the range of from about 400 eV to 1000 eV.15. The process of claim 1 wherein the energy level of the second beamof inert atoms of step b) is in the range of 0.5 KeV to 50 KeV to causea sputtering beam energy of about 1-50 eV/atom.
 16. The process of claim1 wherein the energy level of step c) is in the range of 0.4 KeV to 200KeV.
 17. The process of claim 1 wherein the energy level of the secondbeam of inert atoms of step b) is in the range of 1 KeV to 2 KeV tocause a sputtering beam energy of about 1-50 eV/atom.
 18. The process ofclaim 1 wherein the lower energy beam of step d) is in the range of 75eV to 200 eV.
 19. The process of claim 1 wherein the energy level ofstep a) is 400 eV to 1000 eV, the energy level of step b) is 0.5 KeV to50 KeV to achieve sputtering in the range of 1-50 eV/atom, the energylevel of step c) is 0.4 KeV to 200 KeV and the energy of step d) is 75eV to 200 eV.
 20. The process of claim 19 wherein the energy level ofstep b) is 1 KeV to 2 KeV.